In this study, terpyridine functionalized phosphazene based metallo-supramolecular polymers were synthesized by three step reaction method. In the first step, 4′-(4-aminophenyl)-2,2′:6′,2′′-terpyridine was synthesized with p-nitro benzaldehyde and 2-acetylpyridine. Then, the monomer containing six terpyridine (TPY) units attached to the phosphazene was prepared from 4′-(4-aminophenyl)-2,2′:6′,2′′-terpyridine and hexachlorocyclotriphosphazene by a condensation reaction. Finally, metallo-supramolecular phosphazene polymers were synthesised with these TPY functional phosphazenes and different transition metal ions (Cu, Co, Ni, and Zn ions). Prepared metallo-supramolecular polymers containing phosphazene unit were investigated by elemental analysis, different spectroscopic methods, energy dispersive X-ray spectrometry (EDX) and thermal analysis techniques. The stimuli-responsive, optoelectronic and spectroscopic properties of the synthesised metallo-supramolecular phosphazene polymers were investigated for external effects with UV–Vis spectroscopy and electro-analytic techniques. In addition, competitive ligand effect on these metallo-supramolecular polymers was examined with ethylenediaminetetraacetic acid (EDTA). The resulting metallo-supramolecular polymers containing phosphazene unit show very fast stimuli-responsive properties, such as 3 s. they also showed a single reversible redox structure resulting from the bonding of homometallic segments to polymer chain. In addition, they showed d-π transition (in the range of λ = 330–550 nm) depending on the metal (Co, Ni and Zn) ion forming the supramolecular structure. The addition of competing EDTA ligands caused the degradation of metallo-supramolecular polymer structures. These metallo-supramolecular phosphazene polymers are a good alternative smart material for opto-electronic, electrochromic, photochromic and intelligent material applications.

在这项研究中，通过三步反应法合成了基于吡啶的官能化的磷腈基金属超分子聚合物。第一步，合成4'-（4-氨基苯基）-2,2'：6'，2''-吡啶并与p-硝基苯甲醛和2-乙酰基吡啶。然后，通过缩合反应由4'-（4-氨基苯基）-2,2'：6'，2''-吡啶和六氯环三磷腈制备包含连接至磷腈的含有六个吡啶基（TPY）单元的单体。最后，使用这些TPY官能磷腈和不同的过渡金属离子（Cu，Co，Ni和Zn离子）合成了金属超分子磷腈聚合物。通过元素分析，不同的光谱学方法，能量色散X射线能谱（EDX）和热分析技术对制备的含磷腈单元的金属超分子聚合物进行了研究。刺激反应，利用紫外可见光谱和电分析技术研究了合成的金属-超分子磷腈聚合物的光电和光谱性质对外部影响。另外，用乙二胺四乙酸（EDTA）检查了对这些金属-超分子聚合物的竞争性配体作用。所得的含磷腈单元的金属-超分子聚合物显示出非常快的刺激响应性，例如3s。它们还显示出由于均金属链段与聚合物链的键合而产生的单一可逆氧化还原结构。此外，它们显示出d-π跃迁（在λ= 330-550 nm范围内），具体取决于形成超分子结构的金属（Co，Ni和Zn）离子。竞争性EDTA配体的加入导致金属-超分子聚合物结构的降解。